Stanley Chi Shing Lai

Electrochemistry of Nanoparticles

Metal nanoparticles (NPs) find widespread application as a result of their unique physical and chemical properties. NPs have generated considerable interest in catalysis and electrocatalysis, where they provide a high surface area to mass ratio and can be tailored to promote particular reaction pathways. The activity of NPs can be analyzed especially well using electrochemistry, which probes interfacial chemistry directly. In this Review, we discuss key issues related to the electrochemistry of NPs. We highlight model studies that demonstrate exceptional control over the NP shape and size, or mass-transport conditions, which can provide key insights into the behavior of ensembles of NPs. Particular focus is on the challenge of ultimately measuring reactions at individual NPs, and relating the response to their structure, which is leading to imaginative experiments that have an impact on electrochemistry in general as well as broader surface and colloid science.

Electrocatalytic Oxidation of Alcohols on Gold in Alkaline Media: Base or Gold Catalysis?

On the basis of a comparison of the oxidation activity of a series of similar alcohols with varying pK(a) on gold electrodes in alkaline solution, we find that the first deprotonation is base catalyzed, and the second deprotonation is fast but gold catalyzed. The base catalysis follows a Hammett-type correlation with pK(a), and dominates overall reactivity for a series of similar alcohols. The high oxidation activity on gold compared to platinum for some of the alcohols is related to the high resistance of gold toward the formation of poisoning surface oxides. These results indicate that base catalysis is the main driver behind the high oxidation activity of many organic fuels on fuel cell anodes in alkaline media, and not the catalyst interaction with hydroxide.

Electro-oxidation of ethanol and acetaldehyde on platinum single-crystal electrodes.

The electrochemical oxidation of ethanol and acetaldehyde in sulfuric acid and perchloric acid were studied at Pt (111), Pt (110), and a number of Pt [n(l11)x(111)] single-crystal electrodes. The oxidation of ethanol shows a marked dependence on the surface structure, roughly increasing as the surface step density increases. The oxidation of acetaldehyde shows a reversed correlation, the activity decreasing with increasing step density. Based on the results obtained here and reported earlier in electrochemical and ultrahigh vacuum literature, a detailed reaction scheme for the ethanol oxidation mechanism is suggested.

Landing and Catalytic Characterization of Individual Nanoparticles on Electrode Surfaces

We demonstrate a novel and versatile pipet-based approach to study the landing of individual nanoparticles (NPs) on various electrode materials without any need for encapsulation or fabrication of complex substrate electrode structures, providing great flexibility with respect to electrode materials. Because of the small electrode area defined by the pipet dimensions, the background current is low, allowing for the detection of minute current signals with good time resolution. This approach was used to characterize the potential-dependent activity of Au NPs and to measure the catalytic activity of a single NP on a TEM grid, combining electrochemical and physical characterization at the single NP level for the first time. Such measurements open up the possibility of studying the relation between the size, structure and activity of catalyst particles unambiguously.

Definitive Evidence for Fast Electron Transfer at Pristine Basal Plane Graphite from High-Resolution Electrochemical Imaging†

After all, its active: High-resolution scanning electrochemical cell microscopy (SECCM) demonstrates that electron transfer at the basal plane of highly oriented pyrolytic graphite (HOPG) is fast. This finding requires radical revision of the current textbook model for HOPG electrochemistry.

Visualizing Zeptomole (Electro)Catalysis at Single Nanoparticles within an Ensemble

The relationship between the structural properties, such as the size and the shape, of a catalytic nanoparticle and its reactivity is a key concept in (electro)catalysis. Current understanding of this relationship is mainly derived from studies involving large ensembles of nanoparticles (NPs). However, the results necessarily reflect the average catalytic behavior of an ensemble, even though the properties of individual particles may vary widely. Here, we demonstrate a novel approach using scanning electrochemical cell microscopy (SECCM) to locate and map the reactivity of individual NPs within an electrocatalytic ensemble, consisting of platinum NPs supported on a single carbon nanotube. Significantly, our studies show that subtle variations in the morphology of NPs lead to dramatic changes in (potential-dependent) reactivity, which has important implications for the design and assessment of NP catalysts. The instrumental approach described is general and opens up new avenues of research in functional imaging, nanoscale electron transfer, and catalysis.

Scanning Electrochemical Cell Microscopy: A Versatile Technique for Nanoscale Electrochemistry and Functional Imaging

Scanning electrochemical cell microscopy (SECCM) is a new pipette-based imaging technique purposely designed to allow simultaneous electrochemical, conductance, and topographical visualization of surfaces and interfaces. SECCM uses a tiny meniscus or droplet, at the end of a double-barreled (theta) pipette, for high-resolution functional imaging and nanoscale electrochemical measurements. Here we introduce this technique and provide an overview of its principles, instrumentation, and theory. We discuss the power of SECCM in resolving complex structure-activity problems and provide considerable new information on electrode processes by referring to key example systems, including graphene, graphite, carbon nanotubes, nanoparticles, and conducting diamond. The many longstanding questions that SECCM has been able to answer during its short existence demonstrate its potential to become a major technique in electrochemistry and interfacial science.

Scanning Electrochemical Cell Microscopy: Theory and Experiment for Quantitative High Resolution Spatially-Resolved Voltammetry and Simultaneous Ion-Conductance Measurements

Scanning electrochemical cell microscopy (SECCM) is a high resolution electrochemical scanning probe technique that employs a dual-barrel theta pipet probe containing electrolyte solution and quasi-reference counter electrodes (QRCE) in each barrel. A thin layer of electrolyte protruding from the tip of the pipet ensures that a gentle meniscus contact is made with a substrate surface, which defines the active surface area of an electrochemical cell. The substrate can be an electrical conductor, semiconductor, or insulator. The main focus here is on the general case where the substrate is a working electrode, and both ion-conductance measurements between the QRCEs in the two barrels and voltammetric/amperometric measurements at the substrate can be made simultaneously. In usual practice, a small perpendicular oscillation of the probe with respect to the substrate is employed, so that an alternating conductance current (ac) develops, due to the change in the dimensions of the electrolyte contact (and hence resistance), as well as the direct conductance current (dc). It is shown that the dc current can be predicted for a fixed probe by solving the Nernst-Planck equation and that the ac response can also be derived from this response. Both responses are shown to agree well with experiment. It is found that the pipet geometry plays an important role in controlling the dc conductance current and that this is easily measured by microscopy. A key feature of SECCM is that mass transport to the substrate surface is by diffusion and, for charged analytes, ion migration which can be controlled and varied quantifiably via the bias between the two QRCEs. For a working electrode substrate this means that charged redox-active analytes can be transported to the electrode/solution interface in a well-defined and controllable manner and that relatively fast heterogeneous electron transfer kinetics can be studied. The factors controlling the voltammetric response are determined by both simulation and experiment. Experiments demonstrate the realization of simultaneous quantitative voltammetric and ion conductance measurements and also identify a general rule of thumb that the surface contacted by electrolyte is of the order of the pipet probe dimensions.

Active Sites for Outer-Sphere, Inner-Sphere, and Complex Multistage Electrochemical Reactions at Polycrystalline Boron-Doped Diamond Electrodes (pBDD) Revealed with Scanning Electrochemical Cell Microscopy (SECCM)

The local rate of heterogeneous electron transfer (HET) at polycrystalline boron-doped diamond (pBDD) electrodes has been visualized at high spatial resolution for various aqueous electrochemical reactions, using scanning electrochemical cell microscopy (SECCM), which is a technique that uses a mobile pipet-based electrochemical cell as an imaging probe. As exemplar systems, three important classes of electrode reactions have been investigated: outer-sphere (one-electron oxidation of ferrocenylmethyltrimethylammonium (FcTMA(+))), inner-sphere (one-electron oxidation of Fe(2+)), and complex processes with coupled electron transfer and chemical reactions (oxidation of serotonin). In all cases, the pattern of reactivity is similar: the entire pBDD surface is electroactive, but there are variations in activity between different crystal facets which correlate directly with differences in the local dopant level, as visualized qualitatively by field-emission scanning electron microscopy (FE-SEM). No evidence was found for enhanced activity at grain boundaries for any of the reactions. The case of serotonin oxidation is particularly interesting, as this process is known to lead to deterioration of the electrodes, because of blocking by reaction products, and therefore cannot be studied with conventional scanning electrochemical probe microscopy (SEPM) techniques. Yet, we have found this system nonproblematic to study, because the meniscus of the scanning pipet is only in contact with the surface investigated for a brief time and any blocking product is left behind as the pipet moves to a new location. Thus, SECCM opens up the possibility of investigating and visualizing much more complex heterogeneous electrode reactions than possible presently with other SEPM techniques.

Impact of Surface Chemistry on Nanoparticle–Electrode Interactions in the Electrochemical Detection of Nanoparticle Collisions

The electrochemical detection of a single nanoparticle (NP) at a support electrode can provide key information on surface chemistry and fundamental electron transfer (ET) properties at the nanoscale. This study employs scanning electrochemical cell microscopy (SECCM) as a fluidic device to both deliver individual citrate-capped gold nanoparticles (AuNPs) and study the interactions between them and a range of alkanethiol-modified Au electrodes with different terminal groups, namely, -COOH, -OH, and -CH3. Single NP collisions were detected through the AuNP-mediated ET reaction of Fe(CN)6(4-/3-) in aqueous solution. The collision frequency, residence time, and current-time characteristics of AuNPs are greatly affected by the terminal groups of the alkanethiol. Methods to determine these parameters, including the effect of the instrument response function, and derive ET kinetics are outlined. To further understand the interactions of AuNPs with these surfaces, atomic force microscopy (AFM) force measurements were performed using citrate-modified Au-coated AFM tips and the same alkanethiol-modified Au substrates in aqueous solution at the same potential bias as for the AuNP collision experiments. Force curves on OH-terminated surfaces showed no repulsion and negligible adhesion force. In contrast, a clear repulsion (on approach) was seen for COOH-terminated surface and adhesion forces (on retract) were observed for both COOH- and CH3-terminated surfaces. These interactions help to explain the residence times and collision frequencies in AuNP collisions. More generally, as the interfacial properties probed by AFM appear to be amplified in NP collision experiments, and new features also become evident, it is suggested that such experiments provide a new means of probing surface chemistry at the nanoscale.